The passage of cathodic current through the acidized aqueous bromate solution (catholyte) leads to a negative shift of the average oxidation degree of Br atoms. It means a distribution of Br-containing species in various oxidation states between -1 and +5, which are mutually transformed via numerous protonation/deprotonation, chemical, and redox/electrochemical steps. This process is also accompanied by the change in the proton (H) concentration, both due to the participation of H ions in these steps and due to the H flux through the cation-exchange membrane separating the cathodic and anodic compartments.
View Article and Find Full Text PDFA series of 5,7-disubstituted 1,4-diazepinoporphyrazinato magnesium(II) and nickel(II) complexes, including two novel compounds, were obtained by metal-templated macrocyclization. A combination of X-ray diffraction, H NMR, UV-vis, and electrochemical analyses allowed us to study their tendency towards H-type dimerization and trace the influence of structural and solvation factors on dimer stability. Based on the physicochemical and theoretical DFT calculation data, it was found that the main binding forces between 6-1,4-diazepinoporphyrazine decks in the dimers were efficient π-π donor-acceptor interactions induced by the interdeck C-H⋯N hydrogen bonds.
View Article and Find Full Text PDFNanosized systems of DOX with antitumor activity on the base of micelle-like particles of amphiphilic thermosensitive copolymers of -vinylpyrrolidone (VP) with triethylene glycol dimethacrylate (TEGDM), and -vinylpyrrolidone and methacrylic acid (MAA) with TEGDM were explored. They were investigated in aqueous solutions by electron absorption spectroscopy, dynamic light scattering and cyclic voltammetry. Experimental data and quantum-chemical modeling indicated the formation of a hydrogen bond between oxygen-containing groups of monomer units of the copolymers and H-atoms of OH and NH groups of DOX; the energies and H-bond lengths in the considered structures were calculated.
View Article and Find Full Text PDFThe hydrogen-bromate flow battery represents one of the promising variants for hybrid power sources. Its membrane-electrode assembly (MEA) combines a hydrogen gas diffusion anode and a porous flow-through cathode where bromate reduction takes place from its acidized aqueous solution: BrO3− + 6 H+ + 6 e− = Br− + 3 H2O (*). The process of electric current generation occurs on the basis of the overall reaction: 3 H2 + BrO3− = Br− + 3 H2O (**), which has been studied in previous publications.
View Article and Find Full Text PDFShunting currents are among the main problems of all-vanadium redox flow battery stacks since, in addition to capacity losses, they cause negative effects associated with the local destruction of electrodes and bipolar plates. The values of both the shunting currents and their destructive effects on materials can be reduced at the battery development stage by adjusting the resistance of the electrolyte supply channels. The solution to this problem can be found using a calculation model for current distribution based on the current balance in the nodes as well as voltage drops and electromotive force in internal circuits according to Kirchhoff's laws.
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